CN1490252A - Industrial waste liquid treatment by nano filtering membrane and material recovery art design - Google Patents
Industrial waste liquid treatment by nano filtering membrane and material recovery art design Download PDFInfo
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- CN1490252A CN1490252A CNA021308748A CN02130874A CN1490252A CN 1490252 A CN1490252 A CN 1490252A CN A021308748 A CNA021308748 A CN A021308748A CN 02130874 A CN02130874 A CN 02130874A CN 1490252 A CN1490252 A CN 1490252A
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Abstract
A method for designing the nano filter membrane to treat industrial sewage and recover the useful substances includes using model to screen the nano filter membrane, determining the separating rule, separating model and membrane polluting rule, using mathematical equations to determine running pressure, flow of concentrated liquid membrane area, the number of membrane modules and arranging mode of membrane modules, predicating the membrane pollution, and designing cooling circulation system and washing system. Its advantages are high recovery rate (more than 80%) and high treating effect (more than 95% for COD and color respectively).
Description
Technical field
The invention belongs to processing of environment protection and industrial effluent and material recycling, particularly a kind of nanofiltration membrane industrial effluent is handled and material reclaims process design method.
Prior art
Up to the present, 1. utilize membrane separation technique to carry out that industrial effluent is handled both at home and abroad and material reclaims technological design and mainly concentrates on micro-filtration, ultrafiltration and reverse osmosis; 2. water treatment is handled, given to the relevant nanofiltration membrane treatment processing method of great majority mainly towards pure water; 3. because the nanofiltration membrane appearance is later, marketable value is just at the early-stage not as microfiltration membrane, ultra-filtration membrane and reverse osmosis membrane height, the particularly application aspect the industrial effluent processing, and relevant nanofiltration membrane industrial effluent is handled and material recovery process design method belongs to blank.Existing utilize the nanofiltration membrane industrial effluent to handle and material reclaims processing method and lacks: the 4. functional relation of penetrating fluid flux and pressure difference, the functional relation of penetrating fluid flux and concentration time, the functional relation of penetrating fluid solute concentration and concentration time, the functional relation of penetrating fluid solute concentration and feed liquor solute concentration, the functional relation of penetrating fluid solute initial concentration and film pressure difference, the concentrated solution temperature changing regularity, funtcional relationship between penetrating fluid flux reduction coefficient and the concentration time t; 5. do not determine the method for working pressure, concentrated solution discharge value, membrane area, nanofiltration membrane component number and nanofiltration membrane component permutation and combination method; 6. the complete process flow that the nanofiltration membrane industrial effluent is handled and material reclaims is not proposed; 7. prediction and cleaning system method of design that relevant cooling recirculation system and nanofiltration membrane are polluted are not proposed.
Summary of the invention
The present invention seeks to:
1 handles fine chemistry industry and pharmaceutical industry separation waste liquor and reclaims valuable substance; 2 fill up processing of nanofiltration membrane industrial effluent and material recovery process design method blank; 3 propose the relational expression between the relevant parameters in processing of nanofiltration membrane industrial effluent and the material recovery technology; 4 propose definite method of working pressure, concentrated solution discharge value, membrane area, nanofiltration membrane component number and nanofiltration membrane component permutation and combination method; 5 propose processing of nanofiltration membrane industrial effluent and material recovery technical process; 6 propose the prediction and the cleaning system method of design of relevant cooling recirculation system and nanofiltration membrane pollution.
Content of the present invention is:
Regard the nanofiltration membrane system as a closed system, its parameters is a state function, adopts non-equilibrium thermodynamics and phenomenological theory to derive nanofiltration membrane treatment industrial effluent separating technology method of design.The impellent of above-mentioned membrane sepn process is pressure difference, potential difference, poor, the temperature head (quaternary system, four kinds of logistics and four kinds of impellents) of concentration gradient, the relationship that can utilize other state parameter in the system and time parameter to try to achieve parameters.
Relation between the main technologic parameters: percolate flux and pressure difference relation; See through the logical mathematical relation with concentration time of liquid; See through liquid solute concentration and concentration time and be mathematical relation preferably; See through liquid solute concentration and feed liquor solute concentration relation; See through the relation of liquid solute concentration and film pressure difference; See through the relation of liquid and nanofiltration concentration time.Use penetrating fluid flux reduction coefficient and film to pollute the definite parameter of resistance as nanofiltration membrane concentration polarization and film pollution level.。
Processing of nanofiltration membrane industrial effluent and material recovery technical process, technological design step, design content, calculation of design parameters method mainly comprise: the test of nanofiltration membrane treatment technological test design and craft, about process object law of segregation, disjunctive model with and concentration polarization and pollution rule obtain nanofiltration membrane separation process calculation, the automatic control of nanofiltration membrane separation technology and support equipment design.
The Processes and apparatus design calculation process
1.1 the main operation operating parameter of nanofiltration membrane.Because the flux of the rejection of nanofiltration membrane and solvent is not only relevant with material, physical and chemical performance, the structure of film, and comprise pump discharge pressure, nanofiltration membrane pressure at both sides in nanofiltration membrane component intake pressure, concentrated solution outlet pressure, the system with main operation operating parameter closely related (1) this pressure of pressure of nanofiltration membrane.The result shows according to experimental study, and pressure rising penetrating fluid flux increases, and the rejection of inorganic solute increases with pressure, and the rejection of organic solute increases with pressure and reduces.(2) the temperature temperature that refers to be filtered liquid is when temperature raises, and osmotic pressure and flux be also along with increase, and the rejection of solute presents different Changing Patterns with solute and film different.(3) the solute concentration solute concentration raises, and osmotic pressure increases, and flux reduces.(4) concentrated solution circulation flux refers to that concentrated solution internal circulating load penetrating fluid flux when concentrated solution circulation flux increases that the unit time passes through the unit membrane area ionogenic solute rejection of (5) pH value that raises is relevant with the pH value.
1.2 nanofiltration technique process parameter design reason computation process.
When utilizing the nanofiltration membrane treatment high-concentration waste liquid, the law of segregation of nanofiltration membrane system, disjunctive model with and concentration polarization and pollution rule all have some exclusive characteristic, they and conventional film separation theorem have a great difference, and its technological process is polluted common control by concentration polarization and film.When utilizing traditional technological design theory to carry out industrial mother liquor nanofiltration membrane treatment, wherein some constant under the feedwater treatment condition is a state function, is a plurality of parameters, as related variables such as concentration time, working pressure, mother liquor water quality
(1) certain component penetrating fluid flux
J′
w＝A[ΔP-(π
2-π
3)]
This formula may be for the constant except that working pressure Δ P, and other parameter is state function, fixs in processing condition one, and the penetrating fluid flux is the polynomial function of concentration time.
(2) solute clearance
Identical with top formula, the parameter in this formula is state function, so the solute clearance also should be state function.
(3) true ratio of desalinization r and apparent ratio of desalinization r
AbsRelation can release by above-mentioned equation:
(4) osmotic pressure
Osmotic pressure π becomes with solute species, strength of solution and temperature, and expression agenda and expression formula are a lot.
π＝ΦRT∑M
i＝ΦRTc
p＝Bx
f
C in the formula
pBe solute volumetric molar concentration, x
fBe the solute molar fraction, Φ is the osmotic pressure coefficient, M
iBe the solute volumetric molar concentration, desirable 0.93 to dilute solution Φ, to the π approximate estimation, the B value of some solutes is seen technical literature.
(5) solute flux J
s
J
s＝B(c’
s-c”
s)＝BΔC
s
B is the perviousness constant of salt, Δ c
sBe film both sides solute concentration difference.
(6) see through liquid solute concentration C
RRelation with concentration time t
By experimental data is returned, can see through liquid solute concentration C in the hope of it
RWith the relationship of concentration time t, below be several examples of chapter 3.
A.C
R=52.319t+603.64, coefficient R
2=0.987
b.C
R＝0.0013t
3-0.0803t
2+2.0149t-2.1632
Coefficient R
2=0.9467
c.C
R＝0.7591t
3-11.679t
2+54.71t-65.469
Coefficient R
2=0.8824
According to the analysis of experimental data result, during the different industrial effluent of nanofiltration membrane treatment, see through liquid solute concentration C as can be seen
RBe mathematical relation preferably with concentration time t, but mathematical relation form difference.
(7) solute transmitance SP
c
FmBe average input concentration, c
pBe solute mean concns in the penetrating fluid.
(8) ratio of desalinization SR or r
(9) rate of recovery R and flow equilibrium
Q
f＝Q
r+Q
P
Q
pFor producing penetrating fluid flow velocity, Q
fBe charging flow velocity, Q
rBe the concentrated solution flow velocity.
(10) enrichment factor CF
(11) percolate flux J
wRelation with pressure difference
A.J
w=10.91 Δ p+2.135, coefficient R
2=0.999
B.J
w=11.06 Δ p+1.256, coefficient R
2=0.997
C.J
w=10.51 Δ p+1.607, coefficient R
2=0.998
D.J
w=10.34 Δ p+1.622, coefficient R
2=0.999
(12) percolate flux J
wRelation with concentration time
a.J
w＝-0.0004t
3+0.0436t
2-1.5532t+19.937
Coefficient R
2=0.943
b.J
w＝-0.0012t
3+0.0751t
2-1.5456t+11.436
Coefficient R
2=0.964
c.J
w＝-1.3681t
2-1.6932t+49.606
Coefficient R
2=0.997
d.J
w＝-0.9688t+11.425
Coefficient R
2=0.920
(13) see through liquid solute concentration C
RRelation with concentration time t
A.C
R=52.319t+603.64, coefficient R
2=0.987
b.C
R＝0.0013t
3-0.0803t
2+2.0149t-2.1632
Coefficient R
2=0.9467
c.C
R＝0.7591t
3-11.679t
2+54.71t-65.469
Coefficient R
2=0.8824
(14) see through liquid solute concentration and feed liquor solute concentration relation
A.C
R=2.3037e
0.002Ci, coefficient R
2=0.986
B.C
R=1.745e
0.0022Ci, coefficient R
2=0.923
(15) see through liquid solute concentration C
RRelation with film pressure difference Δ p
A.C
R=121.0ge
-1.5863 Δ p, coefficient R
2=0.974
B.C
R=2439.3e
-1.083 Δ p, coefficient R
2=0.976
Basic design content
All there is a whole set of software separately in some big film companies, supply engineering design usefulness, and output and quality that requirement had both guaranteed to produce water guarantee that again dense water has certain flow rate and concentration range, to reduce the fouling of polluting, realize the operation of long-term safety, economy.
1 provides this average water flux when comprising different water inlet of design limit scope, water flux year decline percentage, the salt transmitance of different film types, the annual growth that salt sees through, the saturation limit of difficulty soluble salt in the dense water, the limit of saturation index, maximum water inlet of element and minimum concentrated stream speed ...
The specific requirement purpose of design of 2 designs is given system parameters, and it will produce the most effective one-tenth the design and economic operation.Normally under the high as far as possible rate of recovery, produce the required water quality and the water yield.Main system parameter: working pressure, the rate of recovery, product water water quality, the product water water yield, average water flux, reverse osmosis units (membrane element number of packages, arrangement mode and operator scheme) etc.
3 basic design processes
(1) sets measure unit and comprise pressure, flow velocity, flux, concentration, temperature
(2) set up new water inlet record (engineering name, code name etc.), input new data influent quality, water source type, composition, ionic concn, pH, temperature, turbidity, SDI, H
2S, Fe, SiO
2, TOC, TDS, specific conductivity, osmotic pressure.
(3) saturation value of data computation and conversion Calculation osmotic pressure, ionic strength, scaling salt, the yin, yang ion of relatively intaking is equivalent balanced, and error is deposited in 10%.
(4) according to water inlet, pre-treatment is set, reach desired SDi.
(5) lay the rate of recovery, establish concentration limit (dense water pH, LSI, ionic strength, the HCO of difficulty soluble salt
3 -, CO
3 2-, CO
2, total alkalinity), determine to transfer pH or with scale inhibitor.
(6) selective membrane component type in conjunction with water inlet, is established annual growth, the water flux of salt transmitance, the year decline percentage of water flux etc.
(7) squeeze into the product water flow velocity, according to the area of membrane element and the water flux parts number of film as can be known, pressurized vessel number etc.; Can provide tentatively according to the rate of recovery etc. that pressurized vessel is arranged and section (level) is several.
(8) calculating program always is that a double counting principle is that intake pressure satisfies the rate of recovery, calculate the performance of first element earlier, its dense water is second element water inlet, calculate second element function ... with all infiltration water additions, compare with target value, regulate intake pressure in view of the above, up to converging to the desired pressure and the rate of recovery, satisfy each limited field requirement simultaneously.
(9) calculation result
1. show flow, pressure, water flux, beta coefficient, product water water quality, dense water saturation;
Alarm display when 2. exceeding design limit;
3. the result outputs to printer;
4. graphic display system flow process; Curve between working pressure, product water water quality, the rate of recovery, the temperature etc.;
5. provide energy consumption and systematic economy cost, pressure, flow, the rate of recovery, efficient and electrical efficiency according to pump draw power of motor; According to the investment, material, labour cost of input, again according to the pertinent data (water production rate, power consumption, membrane element, reagent dosage etc.) of design part, can calculate the cost that produces water.
Optimization of design and design alternative
Basic design;
Penetrating fluid mixes with partial concentration liquid;
The penetrating fluid throttling
Interstage pumps is set;
The circulation of partial concentration liquid;
Secondary (two sections) RO system;
Aftertreatment: the pH regulator and the degassing etc.
Pretreatment system
The trade effluent complicated component can produce precipitation in the nanofiltration process, and the meeting polluted membrane can damage film etc., in order to ensure normally carrying out of nanofiltration process, must carry out pre-treatment to water inlet.Pretreated purpose is generally: 1. remove suspended solids, reduce turbidity; 2. suppress and control the precipitation of slightly soluble salt; 3. regulate and control the temperature and the pH of water inlet; 4. kill and suppress microbial growth; 5. remove various organism; 6. prevent precipitation of metal oxides such as iron, manganese and silicon-dioxide etc.
Have only conscientious pre-treatment, make influent quality meet reverse osmosis and nanofiltration process requirement, then process could normally be carried out, and seldom pollutes, seldom clean, and accident seldom, membrane lifetime is long, and product water water quality is good.If pre-treatment did not reach range request, then consequence is serious.
Remove suspended solids and colloid, reduce turbidity
Suspended solids comprises the oxide compound of mud, iron and corrosion product, MnO
2, throw out, the Al (OH) relevant with hardness
3Throw out, SiO
2, fine sandstone, diatom, bacterium, organic colloid etc.Wherein colloid is the most difficult, and most of colloids are charged, and its homocharge is repelled and stably suspended in water, and its Zeta potential of stable colloid is much when this class colloid condense is on the film surface, then to cause the pollution of film in-30mV, and its rate of setting equation is
Square being directly proportional of pollution speed and colloid concentration.Adopt in the reverse osmosis pre-treatment and silt the quality that density index (SDI) is judged water inlet up, SDI is exactly that a kind of of colloid and particulate loading measures.It is that into water silts by 0.45 μ m Millipore filter membrane that speed calculates out up under the pressure of 207kPa.Usually reverse osmosis requires SDI＜3 of water inlet.The SDI of well water＜1, so needn't carry out the colloidal pre-treatment, the SDI of surface water need conscientiously carry out pre-treatment targetedly at 10-175.
Remove suspended substance and colloidal method
1 online flocculation-multi-medium filtering adds flocculation agent in former water, through effectively mixing, remove little flocs unit of formation again by pressure type multimedium condenser, its effect depends on that kind, concentration, the suitable mixing and the collection of flocculation agent stay the time etc., this should be through test in place, final optimization pass.Should strictly monitor simultaneously, the border situation is adjusted factually.Flocculation agent has FeCl
3, alum, polymerize aluminum chloride and polycation type flocculation agent.Use the aluminium agent to it should be noted that its throw out has minimum solubleness in pH6.5～6.7; Polycation flocculation agent advantage is that the throw out that forms is few, can be broken when filtering, and to not too strictness etc. of the requirement of pH, but should strict control dosage, if excessive meeting causes irreversible damage to film.
Dosage when making Zeta potential approach zero is an optimal coagulant dose, and this moment, SDI was minimum.To chalybeate and aluminium agent, dosage is 10～30mg/L usually, and the polycation flocculation agent is 2～4mg/L.Can add separately, also available mixed flocculation agent is as 5: 1～2: 1 aluminium agent and polycation flocculation agent.
The selection of filtration medium also is very crucial, and AGR (a kind of anhydrous aluminium silicate), sea green sand, sand-hard coal (two medium) and multimedium (can reach 5 kinds) etc. are respond well filtration mediums.
Typical online condensing process is included in and drops into condensing agent in the raw water, mixes effectively and directly removes little flocs unit of formation by the pressure type media filter.Filtering details is referring to water treatment handbook commonly used.
If the use of back recover materials is handled in the flocculation agent that adds influence, then can only adopt filtration method to remove suspended substance and colloidal method.
2 micro-filtrations (MF) and ultrafiltration (UF) (consulting micro-filtration and ultrafiltration relative section) MF and (or) pre-treatment of UF method, advantage is to remove wide ranges, comprises colloid; But operate continuously, excellent property, effluent quality are good, and be good to the protectiveness of high-pressure pump and reverse osmosis; Usefulness or not with medicament less, physical disinfection safety; Invest, take up an area of less, manually economize etc., continuous Microfiltration (CMC) the polypropylene hollow fiber assemblies of using aperture 0.2 μ m more, the device that can clean automatically with two covers gets final product continuous production.Continuous ultrafiltration, the device of then using the hollow-fiber module of molecular weight cut-off (MWCO) 50,000 to make carries out, and filter effect is not worse than CMC's.
Microbial contamination and control
Ground water is one of biological pollution source, and in transmittance process, microorganism also moves and be adsorbed on the film and breeding to face; Excessive flocculation agent, as, SHMP is a nutritive substance, can promote microbial reproduction; Chlorine can make humic acid decompose, and also becomes nutritive substance; Oil and hydro carbons also are easily to cause microorganism growth
The microbial contamination meeting forms the dense gel layer, can adsorb the ion of high density, makes concentration polarization more serious, reduces the mixed effect that flows, simultaneously because the effect of enzyme also can promote the degraded and the hydrolysis of film.This process is slowly, shows that flux descends gradually, and decreasing ratio descends and the increase gradually of pressure drop gradually.Total increasing sharply of bacterial count is one of feature of microbial contamination in the dense water, and the complete failure film is analyzed, and analyzes the existence of bacterial number, kind and susceptible of proof microbial contaminations such as TOC, albumen, ATP and candy.
The reason that causes microbial contamination mainly contains: the water inlet pre-treatment is bad, temperature height, SDI height, organic and inorganic nutrients substrate concentration height and remaining a large amount of bacteriums etc.; Actual pipeline is long, and printing opacity has the dead angle, and the crack is arranged, and non-sterilization section etc. is arranged; Often do not detect low flow velocity, the reagent that long-term storage and use have been polluted etc. in the operation.
Sterilization and disinfection is the main method that prevents microbial contamination, generally is to use the chlorination sterilization, and the chlorine residue of water should remain on 0.5～1mg/L in the system before reverse osmosis units, can prevent microbial reproduction.
To the fragrant polyamide film (composite membrane or asymmetric tubular fibre etc.) of awns, its resistance to chlorine is poor, should make it to satisfy service requirements with gac or sodium bisulfite dechlorination, as＜0.1mg/L etc.
Cellulose acetate class film, under the condition of the chlorine residue of 0.2～0.5mg/L and pH=6, membrane lifetime can be for 3 years, and under the water inlet condition of no free chlorine, bacterium can make film complete failure in more than ten days, this point should be specifically noted that.
High-concentration waste liquid nanofiltration membrane separation Processes and apparatus design process
The nanofiltration membrane separation technological design is owing to the different high-concentration industrial waste liquid in source, and its composition, change of properties are very big, and processing target also has nothing in common with each other, and therefore must at first carry out the nanofiltration membrane separation technological design before each nanofiltration membrane separation technological design.
Technological design
A. at first wish the target selection technology film that reaches according to the character of industrial effluent with after handling.General major consideration is: molecular weight, the chemical property of main dissolved substance (solute) and solvent (as water or n-Octanol etc.) in the industrial effluent, the separating ranges of nanofiltration membrane, applicable elements, structure formation, performance and price (producing producer by nanofiltration membrane dirt provides).A general minimum tubular type or the rolled membrane module selected, experimental scale is pilot scale.
B. select pretreatment process according to the requirement of nanofiltration membrane manufacturer.
C. general nanofiltration membrane process schematic representation and major equipment are seen Fig. 1.
The technology operating procedure
A. pending waste material liquid is squeezed into the concentrated solution storage tank with pump through coarse filter;
B. close blow-off valve and efflux valve, open all valves on the recycle system, open low-pressure pump;
C. open high-pressure pump; Regulated valve is controlled concentrated solution circular flow and membrane module front and back pressure on request;
D. write down different time under meter and micro-flowmeter numerical value;
E. the every index of analytical test different time concentrated solution and penetrating fluid;
F. become very hour when permeate flow, stopper film filters.
The nanofiltration membrane separation process calculation
Determining of main operation operating parameter pressure, concentrated solution discharge value
Determining of A, working pressure
Determining of B, concentrated solution discharge value
Definite membrane area of C, membrane area, component count, membrane module arrangement mode calculates
At first utilize formula to calculate, determine ultimate value then according to actual needs, calculate the longest concentration time at different concentration time penetrating fluid concentration and penetrating fluid flux reduction coefficient.Suppose when t=10 hour the penetrating fluid concentration C
RBe 11.21mg/L, m
wBe 0.86 for ultimate value, then concentration time is defined as 10 hours.
Units of Account area nanofiltration membrane is a permeate production in 10 hours at concentration time.
D, nanofiltration membrane component number
E, nanofiltration membrane component permutation and combination method
Determine that the nanofiltration membrane component arrangement mode need consider factors such as the operational conditions of energy-conservation, nanofiltration membrane, cleaning, the loss of nanofiltration membrane film.Advise adopting one of following three kinds of patterns: consider three sections series-parallel systems of factors suggestion employing such as investment and running cost.
F, cooling recirculation system design
The design key of cooling recirculation system is that type selecting, the concentrated solution of heat exchanger requires temperature range, coolant temperature, concentrated solution flow velocity.Concentrated solution is imported and exported and is established temp probe, cooling fluid is imported and exported and established electrically-controlled valve, electrically-controlled valve according to the control of concentrated solution out temperature probe detected value.
Prediction that G, nanofiltration membrane are polluted and cleaning system design
A. the pollution of the prediction nanofiltration membrane of nanofiltration membrane pollution can be used formula f
2(t) and f
6(t) prediction.General as penetrating fluid flux J
wBe 10% of beginning flux, both m
w=0.9 o'clock, can determine that the nanofiltration membrane pollution level is more serious, concentrating the industrial effluent process should stop.Generally at first utilize formula f
6(t) determine concentration time, utilize formula f
2Penetrating fluid flux when (t) determining that concentration process stops.
B. nanofiltration membrane cleaning system design
It is 0.2% nitric acid or phosphoric acid that nanofiltration membrane can adopt concentration under following clean-out system: a, the 0 ℃ of temperature; Concentration is 0.2% sodium hydroxide under b, the 50 ℃ of temperature; Concentration is 0.5% anion surfactant, for example sodium lauryl sulphate under c, the 45 ℃ of temperature; Concentration is 0.5% coordination agent, for example ethylenediamine tetraacetic acid (EDTA) 4 sodium salts under d, the 5 ℃ of temperature; The washing composition of e .5%-1%, phthalic acid for example, P3Ultrasil 53,75, and 81,91.
Cleaning step: washing → clean-out system is washed → is washed.30 ℃ of cleaning experiment control condition: a, temperature; B, pH:10; C, cleaning last: 0.5 hour; D, pressure: 5atm.Cleaning equipment is by 1) cleaning case; 2) scavenging pump; 3) clean strainer with security personnel; 4) cleaning case well heater; 5) control instruments is formed.
The invention beneficial effect:
(1) disjunctive model mathematics coefficient R
2＞0.90;
(2) the valuable substance rate of recovery＞80%;
(3) COD clearance＞95%;
(4) chroma removal rate＞95%;
(5) cycles of concentration＞10.
Description of drawings
Fig. 1 nanofiltration membrane test technology synoptic diagram
Fig. 2 nanofiltration membrane component synoptic diagram in parallel
Two sections series-parallel connection synoptic diagram of Fig. 3 nanofiltration membrane component
Fig. 4. three sections series-parallel connection synoptic diagram of nanofiltration membrane component
Fig. 5 nanofiltration membrane treatment process schematic representation
Among the figure: 1. nanofiltration membrane component; 2. concentrated solution discharge meter; 3. permeate flow meter; 4. high-pressure pump; 5. tensimeter behind the film; 6. tensimeter before the film; 7. security personnel's strainer; 8. low-pressure pump; 9. concentrate liquid bath; 10. infiltration liquid bath; 11 heat exchangers; 12 concentrate liquid bath; 13 infiltration liquid baths; 14 rinse baths; 15 low-pressure pumps; 16 high-pressure pump; 17 under meters; 18 pipe valves; 19 tensimeters; 20 nanofiltration membrane components
The concrete steps that carry out an invention
(1) at first determines following content according to patent
A. determine to handle the nanofiltration membrane model of high-concentration waste liquid, intact film forming screening operation;
B. the functional relation of penetrating fluid flux and pressure difference
C. the functional relation of penetrating fluid flux and concentration time;
D. the functional relation of penetrating fluid solute concentration and concentration time t;
E. the functional relation of penetrating fluid solute concentration and feed liquor solute concentration;
F. the functional relation of penetrating fluid solute initial concentration and film pressure difference;
G. concentrated solution temperature changing regularity;
H. the funtcional relationship between penetrating fluid flux reduction coefficient and the concentration time;
(2) determine working pressure
(3) determine the concentrated solution discharge value
(4) calculate membrane area
(5) determine the nanofiltration membrane component number
(6) determine the nanofiltration membrane component permutation and combination method
(7) carry out the cooling recirculation system design
(8) prediction of nanofiltration membrane pollution and cleaning system design
(9) carry out processing and manufacturing according to design paper.
Claims (1)
1, a kind of nanofiltration membrane industrial effluent is handled and material recovery process design method, it is characterized in that: regard the nanofiltration membrane system as a closed system, its parameters is a state function, adopts non-equilibrium thermodynamics and phenomenological theory to derive nanofiltration membrane treatment industrial effluent separating technology method of design; The impellent of above-mentioned membrane sepn process is pressure difference, potential difference, poor, the temperature head of concentration gradient, i.e. quaternary system, four kinds of logistics and four kinds of impellents, the relationship that can utilize other state parameter in the system and time parameter to try to achieve parameters; Relation between the main technologic parameters: percolate flux and pressure difference relation; See through the logical mathematical relation with concentration time of liquid; See through liquid solute concentration and concentration time and be mathematical relation preferably; See through liquid solute concentration and feed liquor solute concentration relation; See through the relation of liquid solute concentration and film pressure difference; See through the relation of liquid and nanofiltration concentration time; Use penetrating fluid flux reduction coefficient and film to pollute the definite parameter of resistance as nanofiltration membrane concentration polarization and film pollution level;
Processing of nanofiltration membrane industrial effluent and material recovery technical process, technological design step, design content, calculation of design parameters method mainly comprise: the test of nanofiltration membrane treatment technological test design and craft, about process object law of segregation, disjunctive model with and concentration polarization and pollution rule obtain nanofiltration membrane separation process calculation, the automatic control of nanofiltration membrane separation technology and support equipment design;
The Processes and apparatus design calculation process
1.1 the main operation operating parameter of nanofiltration membrane.Because the flux of the rejection of nanofiltration membrane and solvent is not only relevant with material, physical and chemical performance, the structure of film, and comprise pump discharge pressure, nanofiltration membrane pressure at both sides in nanofiltration membrane component intake pressure, concentrated solution outlet pressure, the system with main operation operating parameter closely related (1) this pressure of pressure of nanofiltration membrane.The result shows according to experimental study, and pressure rising penetrating fluid flux increases, and the rejection of inorganic solute increases with pressure, and the rejection of organic solute increases with pressure and reduces.(2) the temperature temperature that refers to be filtered liquid is when temperature raises, and osmotic pressure and flux be also along with increase, and the rejection of solute presents different Changing Patterns with solute and film different.(3) the solute concentration solute concentration raises, and osmotic pressure increases, and flux reduces.(4) concentrated solution circulation flux refers to that concentrated solution internal circulating load penetrating fluid flux when concentrated solution circulation flux increases that the unit time passes through the unit membrane area ionogenic solute rejection of (5) pH value that raises is relevant with the pH value.
1.2 nanofiltration technique process parameter design reason computation process.
When utilizing the nanofiltration membrane treatment high-concentration waste liquid, the law of segregation of nanofiltration membrane system, disjunctive model with and concentration polarization and pollution rule all have some exclusive characteristic, they and conventional film separation theorem have a great difference, and its technological process is polluted common control by concentration polarization and film.When utilizing traditional technological design theory to carry out industrial mother liquor nanofiltration membrane treatment, wherein some constant under the feedwater treatment condition is a state function, is a plurality of parameters, as related variables such as concentration time, working pressure, mother liquor water quality
(1) certain component penetrating fluid flux
J′
w＝A[ΔP-(π
2-π
3)]
This formula may be for the constant except that working pressure Δ P, and other parameter is state function, fixs in processing condition one, and the penetrating fluid flux is the polynomial function of concentration time.
(2) solute clearance
Identical with top formula, the parameter in this formula is state function, so the solute clearance also should be state function.
(3) true ratio of desalinization r and apparent ratio of desalinization r
AbsRelation can release by above-mentioned equation:
(4) osmotic pressure
Osmotic pressure π becomes with solute species, strength of solution and temperature, and expression agenda and expression formula are a lot.
π＝ΦRT∑M
i＝ΦRTc
p＝Bx
f
C in the formula
pBe solute volumetric molar concentration, x
fBe the solute molar fraction, Φ is the osmotic pressure coefficient, M
iBe the solute volumetric molar concentration, desirable 0.93 to dilute solution Φ, to the π approximate estimation, the B value of some solutes is seen technical literature.
(5) solute flux J
s
J
s＝B(c’
s-c”
s)＝BΔC
s
B is the perviousness constant of salt, Δ c
sBe film both sides solute concentration difference.
(6) see through liquid solute concentration C
RRelation with concentration time t
By experimental data is returned, can see through liquid solute concentration C in the hope of it
RWith the relationship of concentration time t, below be several examples of chapter 3.
A.C
R=52.319t+603.64, coefficient R
2=0.987
b.C
R＝0.0013t
3-0.0803t
2+2.0149t-2.1632
Coefficient R
2=0.9467
c.C
R＝0.7591t
3-11.679t
2+54.71t-65.469
Coefficient R
2=0.8824
According to the analysis of experimental data result, during the different industrial effluent of nanofiltration membrane treatment, see through liquid solute concentration C as can be seen
RBe mathematical relation preferably with concentration time t, but mathematical relation form difference.
(7) solute transmitance SP
c
FmBe average input concentration, c
PBe solute mean concns in the penetrating fluid.
(8) ratio of desalinization SR or r
(9) rate of recovery R and flow equilibrium
Q
f＝Q
r+Q
P
Q
pFor producing penetrating fluid flow velocity, Q
fBe charging flow velocity, Q
rBe the concentrated solution flow velocity.
(10) enrichment factor CF
(11) percolate flux J
wRelation with pressure difference
A.J
w=10.91 Δ p+2.135, coefficient R
2=0.999
B.J
w=11.06 Δ p+1.256, coefficient R
2=0.997
C.J
w=10.51 Δ p+1.607, coefficient R
2=0.998
D.J
w=10.34 Δ p+1.622, coefficient R
2=0.999
(12) percolate flux J
wRelation with concentration time
a.J
w＝-0.0004t
3+0.0436t
2-1.5532t+19.937
Coefficient R
2=0.943
b.J
w＝-0.0012t
3+0.0751t
2-1.5456t+11.436
Coefficient R
2=0.964
c.J
w＝-1.3681t
2-1.6932t+49.606
Coefficient R
2=0.997
d.J
w＝-0.9688t+11.425
Coefficient R
2=0.920
(13) see through liquid solute concentration C
RRelation with concentration time t
A.C
R=52.319t+603.64, coefficient R
2=0.987
b.C
R＝0.0013t
3-0.0803t
2+2.0149t-2.1632
Coefficient R
2=0.9467
c.C
R＝0.7591t
3-11.679t
2+54.71t-65.469
Coefficient R
2=0.8824
(14) see through liquid solute concentration and feed liquor solute concentration relation
A.C
R=2.3037e
0.002Ci, coefficient R
2=0.986
B.C
R=1.745e
0.0022Ci, coefficient R
2=0.923
(15) see through liquid solute concentration C
RRelation with film pressure difference Δ p
A.C
R=121.08e
-1.5863 Δ p, coefficient R
2=0.974
B.C
R=2439.3e
-1.083 Δ p, coefficient R
2=0.976
1 basic design content
Provide this average water flux when comprising different water inlet of design limit scope, water flux year decline percentage, the salt transmitance of different film types, the annual growth that salt sees through, the saturation limit of difficulty soluble salt in the dense water, the limit of saturation index, maximum water inlet of element and minimum concentrated stream speed;
The specific requirement of 2 designs
Purpose of design is given system parameter, and it will produce the most effective one-tenth the design and economic operation; Normally under the high as far as possible rate of recovery, produce the required water quality and the water yield; Main system parameter: working pressure, the rate of recovery, product water water quality, the product water water yield, average water flux, reverse osmosis units, membrane element number of packages, arrangement mode and operator scheme;
3 basic design processes
(1) sets measure unit and comprise pressure, flow velocity, flux, concentration, temperature
(2) set up new water inlet record, input new data influent quality, water source type, composition, ionic concn, pH, temperature, turbidity, SDI, H
2S, Fe, SiO
2, TOC, TDS, specific conductivity, osmotic pressure;
(3) saturation value of data computation and conversion Calculation osmotic pressure, ionic strength, scaling salt, the yin, yang ion of relatively intaking is equivalent balanced, error in 10%,
(4) according to water inlet, pre-treatment is set, reach desired SDi;
(5) lay the rate of recovery, establish the concentration limit of difficulty soluble salt, dense water pH, LSI, ionic strength, HCO
3 -, CO
3 2-, CO
2, total alkalinity, determine to transfer pH or with scale inhibitor;
(6) selective membrane component type in conjunction with water inlet, is established annual growth, the water flux of salt transmitance, the year decline percentage of water flux;
(7) squeeze into the product water flow velocity, according to the area of membrane element and the water flux parts number of film as can be known, pressurized vessel number; Can tentatively provide pressurized vessel according to the rate of recovery arranges and section, progression;
(8) calculating program always is that a double counting principle is that intake pressure satisfies the rate of recovery, calculate the performance of first element earlier, its dense water is second element water inlet, calculate second element function ... with all infiltration water additions, compare with target value, regulate intake pressure in view of the above, up to converging to the desired pressure and the rate of recovery, satisfy each limited field requirement simultaneously;
(9) calculate the result and 1. show flow, pressure, water flux, beta coefficient, product water water quality, dense water saturation; Alarm display when 2. exceeding design limit; 3. the result outputs to printer; 4. graphic display system flow process; Curve between working pressure, product water water quality, the rate of recovery, the temperature; 5. provide energy consumption and systematic economy cost, pressure, flow, the rate of recovery, efficient and electrical efficiency according to pump draw power of motor; According to the investment, material, labour cost of input, again according to the pertinent data of design part: water production rate, power consumption, membrane element, reagent dosage, can calculate the cost that produces water;
4 pretreatment systems
The trade effluent complicated component can produce precipitation in the nanofiltration process, and the meeting polluted membrane can damage film, in order to ensure normally carrying out of nanofiltration process, must carry out pre-treatment to water inlet; Pretreated purpose is generally: 1. remove suspended solids, reduce turbidity; 2. suppress and control the precipitation of slightly soluble salt; 3. regulate and control the temperature and the pH of water inlet; 4. kill and suppress microbial growth; 5. remove various organism; 6. prevent the precipitation of iron, manganese metal oxide and silicon-dioxide;
4.1 remove suspended solids and colloid, reduce turbidity: suspended solids comprises the oxide compound of mud, iron and corrosion product, MnO
2, throw out, the Al (OH) relevant with hardness
3Throw out, SiO
2, fine sandstone, diatom, bacterium, organic colloid;
Square being directly proportional of pollution speed and colloid concentration; Adopt in the reverse osmosis pre-treatment and silt the quality that density index SDI judges water inlet up, SDI is exactly that a kind of of colloid and particulate loading measures; It is that into water silts by 0.45 μ m Millipore filter membrane that speed calculates out up under the pressure of 207kPa; Usually reverse osmosis requires SDI＜3 of water inlet; The SDI of well water＜1, so needn't carry out the colloidal pre-treatment, the SDI of surface water need conscientiously carry out pre-treatment targetedly at 10-175;
In former water, add flocculation agent 4.2 remove the 1. online flocculation-multi-medium filtering of suspended substance and colloidal method, through effectively mixing, remove little flocs unit of formation again by pressure type multimedium condenser, its effect depends on that kind, concentration, the suitable mixing and the collection of flocculation agent stay the time, this should be through test in place, final optimization pass; Should strictly monitor simultaneously, the border situation is adjusted factually; Flocculation agent has FeCl
3, alum, polymerize aluminum chloride and polycation type flocculation agent; Use the aluminium agent to it should be noted that its throw out has minimum solubleness in pH6.5～6.7; Polycation flocculation agent advantage is that the throw out that forms is few, can be broken when filtering, and not too strict to the requirement of pH, but answer strict control dosage, if excessive meeting causes irreversible damage to film;
Dosage when making Zeta potential approach zero is an optimal coagulant dose, and this moment, SDI was minimum; To chalybeate and aluminium agent, dosage is 10～30mg/L usually, and the polycation flocculation agent is 2～4mg/L; Can add separately, also available mixed flocculation agent is as 5: 1～2: 1 aluminium agent and polycation flocculation agent;
The selection of filtration medium also is very crucial, and it is respond well filtration medium that AGR anhydrous aluminium silicate, sea green sand, the two media of sand-hard coal and multimedium can reach 5 kinds;
Typical online condensing process is included in and drops into condensing agent in the raw water, mixes effectively and directly removes little flocs unit of formation by the pressure type media filter; Filtering details is referring to water treatment handbook commonly used;
If the use of back recover materials is handled in the flocculation agent that adds influence, then can only adopt filtration method to remove suspended substance and colloidal method; 2. micro-filtration MF and ultrafiltration UFMF and the pre-treatment of UF method, advantage is to remove wide ranges, comprises colloid; But operate continuously, excellent property, effluent quality are good, and be good to the protectiveness of high-pressure pump and reverse osmosis; Usefulness or not with medicament less, physical disinfection safety; Invest, take up an area of less, manually economize, continuous Microfiltration CMC uses the polypropylene hollow fiber assembly of aperture 0.2 μ m more, and the device that can clean automatically with two covers gets final product continuous production; Continuous ultrafiltration then carries out with the device that the hollow-fiber module of molecular weight cut-off MWCO5 ten thousand is made, and filter effect is not worse than CMC's;
4.3 microbial contamination and control
Ground water is one of biological pollution source, and in transmittance process, microorganism also moves and be adsorbed on the film and breeding to face; Excessive flocculation agent, as, SHMP is a nutritive substance, can promote microbial reproduction; Chlorine can make humic acid decompose, and also becomes nutritive substance; Oil and hydro carbons also are easily to cause microorganism growth;
The microbial contamination meeting forms the dense gel layer, can adsorb the ion of high density, makes concentration polarization more serious, reduces the mixed effect that flows, simultaneously because the effect of enzyme also can promote the degraded and the hydrolysis of film; This process is slowly, shows that flux descends gradually, and decreasing ratio descends and the increase gradually of pressure drop gradually;
Total increasing sharply of bacterial count is one of feature of microbial contamination in the dense water, and the complete failure film is analyzed, and analyzes the existence of bacterial number, kind and TOC, albumen, ATP and the microbial contamination of candy susceptible of proof;
The reason that causes microbial contamination mainly contains: the water inlet pre-treatment is bad, temperature height, SDI height, organic and inorganic nutrients substrate concentration height and remaining a large amount of bacterium; Actual pipeline is long, and printing opacity has the dead angle, and the crack is arranged, and non-sterilization section is arranged; Often do not detect low flow velocity, the reagent that long-term storage and use have been polluted in the operation;
Sterilization and disinfection is the main method that prevents microbial contamination, generally is to use the chlorination sterilization, and the chlorine residue of water should remain on 0.5～1mg/L in the system before reverse osmosis units, can prevent microbial reproduction;
To the fragrant polyamide film of awns, composite membrane or asymmetric tubular fibre, its resistance to chlorine is poor, should make it to satisfy service requirements with gac or sodium bisulfite dechlorination, as＜0.1mg/L;
Cellulose acetate class film, under the condition of the chlorine residue of 0.2～0.5mg/L and pH=6, membrane lifetime can be for 3 years, and under the water inlet condition of no free chlorine, bacterium can make film complete failure in more than ten days;
High-concentration waste liquid nanofiltration membrane separation Processes and apparatus design process
1 nanofiltration membrane separation technological design is owing to the different high-concentration industrial waste liquid in source, and its composition, change of properties are very big, and processing target also has nothing in common with each other, and therefore must at first carry out the nanofiltration membrane separation technological design before each nanofiltration membrane separation technological design;
1.1 technological design
A. at first wish the target selection technology film that reaches according to the character of industrial effluent with after handling; General major consideration is: main dissolved substance in the industrial effluent, solute and solvent: the molecular weight of water or n-Octanol, chemical property, the separating ranges of nanofiltration membrane, applicable elements, structure formation, performance; A general minimum tubular type or the rolled membrane module selected, experimental scale is pilot scale;
B. select pretreatment process according to the requirement of nanofiltration membrane manufacturer; 1.2 technology operating procedure
A. pending waste material liquid is squeezed into the concentrated solution storage tank with pump through coarse filter;
B. close blow-off valve and efflux valve, open all valves on the recycle system, open low-pressure pump;
C. open high-pressure pump; Regulated valve is controlled concentrated solution circular flow and membrane module front and back pressure on request;
D. write down different time under meter and micro-flowmeter numerical value;
E. the every index of analytical test different time concentrated solution and penetrating fluid;
F. become very hour when permeate flow, stopper film filters;
Determining of 2 nanofiltration membrane separation process calculation, 2.1 main operation operating parameter pressure, concentrated solution discharge value
Determining of A, working pressure
Determining of B, concentrated solution discharge value
Determining of C, membrane area, component count, membrane module arrangement mode, membrane area calculates and at first utilizes formula to calculate at different concentration time penetrating fluid concentration and penetrating fluid flux reduction coefficient, determine ultimate value then according to actual needs, calculate the longest concentration time; Suppose when t=10 hour the penetrating fluid concentration C
RBe 11.21mg/L, m
wBe 0.86 for ultimate value, then concentration time is defined as 10 hours; Units of Account area nanofiltration membrane is a permeate production in 10 hours at concentration time;
D, nanofiltration membrane component number
E, nanofiltration membrane component permutation and combination method
Determine that the nanofiltration membrane component arrangement mode need consider energy-conservation, the operational conditions of nanofiltration membrane, cleaning, nanofiltration membrane film loss factor; Adopt one of following three kinds of patterns: all in parallel, two sections series-parallel connection, three sections series-parallel connection,
The design key of F, cooling recirculation system design cooling recirculation system is that type selecting, the concentrated solution of heat exchanger requires temperature range, coolant temperature, concentrated solution flow velocity; Concentrated solution is imported and exported and is established temp probe, cooling fluid is imported and exported and established electrically-controlled valve, electrically-controlled valve according to the control of concentrated solution out temperature probe detected value;
Prediction that G, nanofiltration membrane are polluted and cleaning system design
A. the prediction of nanofiltration membrane pollution
The pollution of nanofiltration membrane can be used formula f
2(t) and f
6(t) prediction; General as penetrating fluid flux J
wBe 10% of beginning flux, both m
w=0.9 o'clock, can determine that the nanofiltration membrane pollution level is more serious, concentrating the industrial effluent process should stop; Generally at first utilize formula f
6(t) determine concentration time, utilize formula f
2Penetrating fluid flux when (t) determining that concentration process stops;
The design of nanofiltration membrane cleaning system
It is 0.2% nitric acid or phosphoric acid that nanofiltration membrane can adopt concentration under following clean-out system: a, the 0 ℃ of temperature; Concentration is 0.2% sodium hydroxide under b, the 50 ℃ of temperature; Concentration is 0.5% anion surfactant, for example sodium lauryl sulphate under c, the 45 ℃ of temperature; Concentration is 0.5% coordination agent, for example ethylenediamine tetraacetic acid (EDTA) 4 sodium salts under d, the 5 ℃ of temperature; The washing composition of e, 5%-1%, phthalic acid for example, P3Ultrasil 53,75, and 81,91;
Cleaning step: washing → clean-out system is washed → is washed;
30 ℃ of cleaning experiment control condition: a, temperature; B, pH:10; C, cleaning last: 0.5 hour; D, pressure: 5atm.
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